Dry cleaning compositions



3,018,251 DRY CLEANING COMPOSITIONS Raymond L. Mayhew, Phillipsburg, andJohn P. Miller III, Bloomfield, N.J., and Marvin Kopp, Lenox, Mass.,assignors to General Aniline & Film Corporation, New York, N.Y., acorporation of Delaware No Drawing. Filed Jan. 11, 1957, Ser. No.633,545 6 Claims. (Cl. 252-152) This invention relates to improvementsin the dry cleaning of fibrous textiles and related materials and moreparticularly to new and improved compositions for use with dry cleaningsolvents, and to processes of dry cleaning wherein said improvedcompositions are employed.

It is well known that many types of fabrics and materials cannot becleaned by the ordinary means of soap or detergents and water, such asare employed in laundering type operations since the presence of waterdeleteriously affects such materials. To provide effective cleaning forsuch materials, a dry cleaning process must be used. Dry cleaningprocesses employ organic solvents which are effective in removing fromthe materials treated most of the undesirable dirt, grease, dust and thelike. It is also a common expedient in dry cleaning processes to add asmall amount of water which, sufficiently dis persed in the dry cleaningfluid, will be effective to remove water-soluble stains withoutadversely affecting the material treated.

It is therefore an object of this invention to provide new compositions,particularly suitable for use in dry cleaning operations.

It is a further object of this invention to provide new compositionssuitable for use in all of the generally employed dry cleaning solvents.

It is a still further object of this invention to provide newcompositions which give outstanding and improved cleaning ability byvirtue of an outstanding detergency action coupled with an excellentability to prevent soil redeposition on the materials treated.

It is another object of this invention to provide an improved process ofdry cleaning in all types of dry cleaning solvents.

It is a further object of this invention to provide an improved processof dry cleaning wherein the usual dry cleaning solvents are employed inconjunction with minor amounts of water.

According to the present invention the new compositions thereof,hereinafter termed dry cleaning compositions, to be incorporated in theusual dry cleaning solvents contain as the essential components thereofa cationic surfactant derived from fatty amines and an alkylene oxideand at least one anionic surfactant. In addition thereto it is desirableto incorporate in the above described mixture an additional surfactantof the nonionic type.

Compositions as above described give particularly outstanding results inall types of dry cleaning solvents. In addition, they give excellentresults where a small amount of water has been incorporated into the drycleaning solvent for the purposes described above. Among the drycleaning solvents one may use and which are normally employed in drycleaning operations are the following:

Gasoline Kerosene Trichloroethylene Tetrachloroethylene Carbontetrachloride Stoddard solvent, and the like The cationic agents whichare contemplated in this invention are derived as described above fromfatty amines reacted with alkylene oxides or their equivalent. The fattyamines which are employed herein are those amines which contain at least75% unsaturated linkages therein,

3,018,251 Patented Jan. 23, 1962 "ice Percent Octadecadienyl amine 45Octadecenyl amine 3S Octadccyl amine 10 Hexadecyl amin 10 It will benoted that this nixture contains 80% unsaturates of which 45% are of thediethenoid type. It is of course possible to employ in the preparationof the compositions of this invention synthetically prepared mixturesfrom the various amines within the scope of this invention and it isfurther possible to employ the pure unsaturated amines provided theycome within the scope of the above limitations. In addition to soybeanamine, numerous other fatty oils are suitable as precursors for theamines operable in this invention. Such fatty oils include cottonseedoil, corn oil, sesame oil, sunflower seed oil and the like. Theapproximate acid constituents of these oils are given below:

Cotton seed oil Amines derived from these oils in the manner of thatdescribed above for soybean amine will contain at least of the amineconstituent as unsaturates of which amount at least 35% will representdoubly unsaturated compounds. In addition to the above mentioned fattyoils it is also possible to employ other naturally occurring materialswhich, upon suitable treatment by hydrolysis, ammonolysis and reduction,yield an amine or mixtures of amines coming within the scope of thelimitations described above as to the unsaturate content thereof. Thecationic agent suitable for use in the compositions of this inventionare prepared from the above described amines or mixtures of amines bywell known reactions with alkylene oxides or their equivalents. Thepolyoxyalkylated products resulting from such processes which aresuitable for use in this invention are those products which contain fromabout 14 to about 53% alkylene oxide or its equivalent (l to 7 moles ofalkylene oxide per mole of amine). Methods for the preparation of suchcondensation products are described in United States Patents 1,970,578and 2,213,477.

The anionic synthetic surfactant to be employed as the second componentof the compositions of this invention include the alkyl aryl sulfonatessuch as sodium keryl benzene sulfonate, diisobutyl naphthalene sulfonicacid and the like, the N-fatty acid acyl-N-alkyl taurates, such assodium-N-oleoyl-N-methyl taurate, sodium-N-lauryl- N-cyclohexyl taurate,and the like, alkyl aryl-polyoxyalkylene salts such as those derivedfrom alkylated aromatic hydroxy compounds of the benzene and naphthaleneseries reacted with 3 to 7 moles of an alkylene oxide or its equivalentand subsequently esterified with a strong acid such as sulfonic,phosphoric or the like. Additionally, anionic salts from the nonionicalkyl aryl polyoxyalkylene glycols described below may be employed.

In addition to the two classes of ingredients described above, that is,the cationic and anionic surfactants, there may be employed in thecomposition a nonionic surfactant of the alkyl aryl polyoxyalkyleneglycol type. These glycol ethers may be derived in the known manner fromalkylated aromatic hydroxy compounds of the benzene and naphthaleneseries such as p-n-butylphenol, amylcresol, diisobutylphenol,diamylphenol, isohexylphenol, oleylphenol, isododecylphenol,tetradecylphenol, isooctylresorcinol, nonylphenol, dinonylphenol,isooctylphenol, isooctyl-fi-naphthol, isohexylxylenol,n-octadecylphenol, and the like. In general, these alkylated aromatichydroxy compounds should contain at least one alkyl radical of at least4 carbon atoms as a ring substituent. It will be understood that suchcompounds may contain up to 3 alkyl substituents which may be straightor branched, which substituents may contain a total of or more carbonatoms.

These alkylaryl hydroxy compounds are polyoxyalkylenated by reactionunder proper conditions, preferably in the presence of an alkalinecatalyst such as potassium hydroxide or sodium hydroxide, and heat andpressure, with from 3 to 7 moles of an alkylene oxide such as ethyleneoxide, propylene oxide, or the like, or mixtures thereof.

The anionic polyoxyalkylene salts described above are readily preparedfrom these nonionic compounds by subjecting said nonionic glycol etherto esterification with a strong acid such as chlorosulfonic, sulfamic,sulfuric, or phosphoric or with an inorganic acid anhydride such assulfur trioxide or phosphorus pentoxide or with acid halides such assulfuryl chloride, phosphorus oxychloride or phosphorus pentachloride orthe like. When a properly substituted acid mixture is employed in theesterification such as aminosulfonic acids, sulfamic acid, ammoniumbisulfate, and the like, a. water-soluble or dispersible salt isdirectly produced without the necessity of subsequent neutralizationwith a basic substance. In such cases, subsequent treatment with basicmaterials is only for the purpose of neutralizing excess acid, and thelike. Excellent results are also obtained when complexes of some of theabove acids and anhydrides are employed. For example, a combination ofsulfur trioxide or chlorosulfonic acid with an ether such as dioxane,thioxane or [3,,8' dichlorodiethylether, or with a tertiary nitrogenbase such as pyridine or triethylamine may be used. The resulting estersmay be neutralized with a basic material such as sodium hydroxide,potassium hydroxide, sodium carbonate, sodium acetate, ammoniumhydroxide, ammonia, calcium oxide and hydroxide, magnesium oxide andhydroxide, strontium hydroxide, cthanolaminc, diethanolamine,triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine,triethylamine, diethylamine, butylamine, propylamine, cyclohexylarnine,morpholine, pyridine, octanolamine, octylamine, and the like.

The greatest values to be derived from this invention lie not only inthe superior detergent action of the dry cleaning compositions thereofbut further, in the outstanding characteristics of soil rcdepositionprevention and whiteness retention which are evident in all types of drycleaning solvents. This is in contrast to the usual detergentcompositions which are suitable for use in only one of the two majortypes of dry cleaning solvent systems. In order to achieve the excellentand superior effects to be derived from the use of the compositions ofthis invention, the proportions of the various ingredients thereof mustbe employed within certain critical limits. The cationic surfactantwhich, as described above, is of the polyoxyalkylated unsaturated aminetype, should comprise at least 25% on a volume basis of the totalsurfactants present, and no more than about 55%. The above describedanionic agents should be employed within the range of 30 to 75% on avolume basis based on the total surfactants present. The nonioniccompounds when present should not exceed on a volume basis 30% of thetotal surfactants. While it is not essential in order to achieveoutstanding results with the compositions of this invention toincorporate a nonionic agent in the majority of formulations, theaddition thereto of nonionics results in compositions of exceptionallyoutstanding properties. The formulations hereinafter described wherespecific data is indicated for detergency action and whiteness retentioncharacteristics were tested as follows:

Into each of 8 pint Mason jars there were introduced- 50 /2 in. steelballs 50 ml. of solvent 1 3 /2 in. diameter circular swatch of acetatejersey or Botany wool flannel, soiled or unsoiled, as indicated below.The 8 jars contained the following:

TABLE 1 Launder-Ometer test components Test Acetate jersey solled swatchDetergency. Wool flannel soiled swatch Do. Acetatie jersey soiledswatch, detergent wet Do.

stoc Wool lflannel soiled swatch, detergent wet Do.

stoc Unsoiled acetate jersey swatch, 5 mg. syn- Itedeposltlon.

thetic dry soil. Unsoiled acetate wool flannel swatch, 5 mg. Do.

synthetic dry soil. Unsoiled acetate jersey swatch, 5 mg. syn- Do.

thetic dry soil, detergent wet stock. Unsolled wool flannel swatch, 5mg. syn- Do.

thetlc dry soil, detergent wet stock.

The synthetic dry soil used in the above tests has the followingcomposition:

TABLE 2.

Synthetic soil composition Ingredients mixed as follows:

The above were mixed in a ball mill until heterogeneous. The oils listedbelow were melted and blended by hand into the powdered mixture. Theywere:

Components Percent Grams stenric acid 1. 6 16.0 olelc acid 1. ti 16. 0palm oil fatty acid (lInrsborn) 3. .5 32. o lnuryl alcohol t). 5 5.1)lanolin unltydride (Merck) 1.0 10.0 m-mrtmlccznn: (Conn. llnrtlltnbhcr). 1.1 ll." l-oetadccenc (Humphrey \l'ilkinuon) 1.1 11. (t

1500 ml. H O were added. The above were mixed in a ball mill for 16hours and dried. The dried soil was then pulverized in a hammer mill toapproximately 200 mesh.

The cloth used for detergcncy tests was soiled by padding in theButterworth three-roll padder, giving 3 passes 6 reacted with 33%ethylene oxide are added to 10 parts of Stoddard solvent (3. petroleumsolvent). The elficiency of the above formulation is set forth in Table3 and a comparison with other commercial dry cleaning dethrough asuspension of the synthetic dry soil in 5 tergents and a controlcontaining no detergent is also Stoddard solvent and air drying thecloth. All cloth was given. stored in a constant humidity chamber priorto use at a In the following table, column 1 indicates the detergentrelatively humid ty of 50 to 63%. tested, column 2 the fabric, which isprepared for the The test conditions were as follows: detergency testsas described above. Column 3 lists Apparatus employed: AtlasLaunder-Ometer (42 rpm.) g sPlvents i 3 1 3 thedeergency gl with waterbath drain to avoid excess moisture F a i Dye age or} re q i g'Temperature: Temperature maintained at room temperae S ta en as amagneslum e :10 ture The unsoiled rayon and wool have varying degrees ofMedium: Stoddard solvent or perchlorethylene5l) cc. (hltemss and f f themgmficam values are the cleaningcycle. min 15 differences appearing incolumns 5 and 7. Thus the Rinse cycle: 15 min., in 50 cc. clean solventlarger g izl .93 1S g g q Control: Appropriate solvent with no detergentadded acne 0 t e e H t e gum.m column 7 the better is the compositionfor preventing In the hQ E examples which W111 serve to mplify soilredeposition. The figures in column 6(a) are the the compositions andprocesses of this invention, it will values obtained for unsoiled,untreated fabrics, those of be understood that such exemplification isnot deemed to column 6(b) the values for the same swatches put throughbe limitative of the invention herein covered. In the a cleaning cycleas indicated in Table 1 for jars 5-8.

TABLE 3 Reflectance Readings Detergency whiteness Retentlon 1 2 3Detergent Fabric Solvent 4 5 6 7 Soiled Cleaned Before After CleaningCleaning rayon L. 51.0 53. 0 2 77.1 57. 5 19.6 32. 0 35. 0 3 63. 0 47. 016. o 52.3 66.0 14.6 77.1 70.0 7.1 34.0 53.3 19.3 62.8 61.0 1.8 40. 760. 5 10. s 77.3 66. 0 11.3 44.5 50.5 6.0 63.5 60.8 12.7 51. 4 66. 7 15.3 77.3 71. 0 6. 3 42.0 60.0 12.0 63.2 61.0 2.2 30. 6 34. 0 3. 4 78.8 58.3 20. 5 24. 0 23. 3 (a) 62. 0 47. 1 14.9 36.0 45.0 0.9 78.0 53.0 20.023. 9 31.1 7. 2 63. 6 55. 5 8.1 34.0 43.0 0.0 77.0 49.6 27.4 24.1 26.01.0 63.9 40.2 14.7 34. 5 1 57.2 22. 7 77. 0 64.0 13. 0 24.6 46.0 22.063.4 57.1 6.3 34.0 43.0 9.0 77.8 70.0 7.0 24.1 26.0 1.9 64.5 56.0 8.534.5 47.2 12.7 77.0 72.1 7.8 24.6 36.0 12.6 64.5 56.1 2.4 34.3 64.0 20.777.4 72.5 4.0 24. 7 37. 0 13. 7 64. 5 57. 5 7. 0 36.2 65.6 20.4 77.767.3 9.0 24.4 48.4 24.0 64.4 57.0 6.5 36. 0 54. 0 l8. 0 70.5 56. 7 13. 823. 7 24. s 1.1 61. 0 40. 0 12.0 36. 7 61. 7 25. 0 70. 3 66. 1 5. 2 22.431.7 0.3 61.0 55.0 6.0 3-1. 1 50. 1 16. 0 77. s 53. 0 24. s 25. 5 32. 26. 7 64. 0 52. 0 12. 0 34. 2 36. 3 1.5 76. 0 50. 0 10.0 25. 3 35. 7 10.4 64. 5 50.9 13. 6

1 Acetate jersey.

2 Wool flannel.

a Stoddard solvent. Perchloroethylene.

5 Useful only in solvent tested. 6 The cleaned wool was not cleaned lnthis test.

7 Fabric badly streaked.

w '1li0seagenls useful only in the solvents tested.

said examples, parts indicates parts on a volume basis unless otherwiseindicated.

EXAMPLE 1 A mixture of 7 parts diisobutyl naphthalene sulfonic acid and2 parts of a cationic surfactant prepared from refined soybean aminehaving the following composition:

' Percent Octadecadienyl amine Octadecenyl amine 35 Octadecyl amine l0Hexadecyl amine 10 Example 1 when tested in Stoddard solvent on rayon001207605902485220000552 6 LZZZOKLA QL 8 4-4L3 &LMMG66H665766576H4756576 oooozvuu n 221 varying pro- Whlteness RetentionBefore Cleaning Cleaning 805293565765901207 033004 &&3 7 Z5 Q&4 0&lomomidflqwomflinhid 1221321112 111 321 32 Percent EXAMPLE 3 EXAMPLE 4Table 4.

Reflectance Readings Cleaned Anionic Agent Parts iven in TABLE 4Detergency Solled TABLE 5 ti parts D 0 Alkylaryl polyoxyethylene glycol3.0 Reaction product of refined soybean amine containing 33% ethyleneoxide 4.0 Sodium keryl benzene sulfonate 3.0

Sodium N-oleoyl-N-methyltaurate. 5 Reaction product of refined soybeanamine containing ethylene oxide (33%).. 6 n-Butanol 1 Petroleum solvent4 Solvent A composition comprising the following ingredients isprepared:

Components:

10 idNgnyl phenoxy polyoxyethylene ethanol (58% ethylene The results aregiven in Table 4.

A composition comprising the following ingredients is 5 prepared:

Components The results are g In the following Examples 5 through 12portions of cationic, anionic and nonionic surfactants are CationicAgent Parts Parts by volume 4.0 1 Diisobutyl naphthalene sulfonic acid1.5

Commercial agent D'with rayon,

EXAMPLE 2 A composition comprising the following ingredients is preparedgives a value of 14.6 in column 5 as opposed to a value of 2.0 for thecontrol. on the other hand, gives a value of 29.4 but this must becompared to the control value of 29.7 which indicates that here thedetergent impaired the normal action of the 5 solvent.

Components:

Alkylaryl polyoxyethylene glycol 3.0 Reaction product of refined soybeanamine containing 33% ethylene oxide Alkylaryl polyoxyethylene sulfate1.5 Petroleum solvent"--- 5.0

:Nonyl phenoxy polyoxyethylene ethanol (58% ethylene ox e).

Ammonium salt of the sulfate ester of nonyl phenoxy (58% ethyleneoxide).

Example Table 4.

l A is rcactionprotluot showing refined soybean ainine containing 33%ethelene oxide.

1 ll isrmtolion product showing refined soybean amine containing 14%ethylene oxide.

3 is react ion nroduot showing refined soyhcanainino containing 53%ethylene oxide.

l) is diisohntyl nuphtlmlonv sulfouic aeidi 5 E is sodium laoryl hem nosullouate.

7 (l is nouyl phon xy polyoxyothylcnc ethanol.

employed. In each instance the results are outstanding in so far asdetergency action is concerned and further, there is excellent soilredeposition prevention.

This invention has been disclosed with respect to certain preferredembodiments. Various modifications and variations of these embodimentswill become apparent to those skilled in the art, and it is to beunderstood that such modifications and variations are to be includedwithin the spirit and purview of this application and the scope of theappended claims.

We claim:

1., A composition adapted for use in the dry cleaning of textile andfibrous materials consisting essentially of a surface active agentmixture for each 100 parts of which there are present at least 25 partsof a polyoxyalkylated dialkenoid fatty amine containing from about 14 toabout 53% alkylene oxide and 30 to 75 parts of an anionic surface activeagent.

2. A composition adapted for use in the dry cleaning of textile andfibrous materials consisting essentially of a surface active agentmixture for each 100 parts of which there are present at least 25 partsof a polyoxyalkylated dialkenoid fatty amine containing from about 14 toabout 53% ethylene oxide and 30 to 75 parts of an anionic surface activeagent selected from the group consisting of alkylaryl sulfonate surfaceactive agents, N-fatty acid acyl-N-alkyl taurate surface active agentsand alkylaryl polyoxyalkylated salt surface active agents and mixturesthereof.

3. A composition adapted for use in the dry cleaning anionic surfaceactive agent is diisobutyl naphthalene sulfonic acid.

5. A composition as defined in claim 3 wherein the anionic surfaceactive agent is a mixture of diisobutyl naphthalene sulfonic acid and analkylaryl polyoxyethylene sulfate.

6. A composition as defined in claim 3 wherein the anionic surfaceactive agent is sodium N-oleoyl-N-methyl taurate.

References Cited in the file of this patent UNITED STATES PATENTS2,271,635 Flett Feb. 3, 1942 2,619,467 'Isbell Nov. 25, 1952 2,677,700Jackson et al. May 4, 1954 2,697,075 Echols Dec. 14, 1954 2,721,847Gebhart et a1 Oct. 25, 1955 2,733,212 Epstein et a1. Jan. 31, 19562,778,814 Behrens et al. Jan. 22, 1957

1. A COMPOSITION ADAPTED FOR USE IN THE DRY CLEANING OF TEXTILE ANDFIBROUS MATERIALS CONSISTING ESSENTIALLY OF A SURFACE ACTIVE AGENTMIXTURE FOR EACH 100 PARTS OF WHICH THERE ARE PRESENT AT LEAST 25 PARTSOF A POLYOXYALKYLATED DIALKENOID FATTY AMINE CONTAINING FROM ABOUT 14 TOABOUT 53% ALKYLENE OXIDE AND 30 TO 75 PARTS OF AN ANIONIC SURFACE ACTIVEAGENT.